General Oxygen Vacancy Engineering by Molten Zinc to Regulate Anode Redox for Durable Aqueous Zinc–Iodine Batteries

Oxygen vacancy engineering plays a crucial role in regulating surface chemistry for managing redox behaviors. However, controllable implantation of oxygen vacancy and safe and cost-effective production remain challenging. Herein, we report a general molten zinc reduction technology to prepare oxygen-deficient oxides with tunable vacancy content, synthetic universality, and industrial compatibility under mildly elevated temperature. Taking TiO₂ as an example, theoretical study demonstrates thermodynamically favorable zinc affinity on TiO₂ with increasing surface coverage supporting molten Zn supply. Featuring favorable electronic structures and inferior hydrogen evolution activity, TiO_2-<i>x</i> nanoparticles were used to decorate aqueous Zn anodes, which demonstrate much improved cycling stability, verified by theoretical and <i>in situ</i> and <i>ex situ</i> investigations. Eventually, zinc-iodine batteries were assembled using modified Zn anodes, which achieved favorable cycling performance due to the regulated anode redox and alleviated self-discharge behaviors. This work provides a general oxygen vacancy engineering technology with an in-depth understanding for durable aqueous zinc batteries and related systems.